Alkyl-substituted aromatic sulphonic acids



Patented June 6, 1939 UNITED STATES gratin PATENT OFFICE-ALKYL-SUBSTITUTED AROMATIC SULPHONIG ACIDS No Drawing. Application July2, 1936, Serial No. 88,685

14 Claims. (01. 260-505) The present invention relates to the use of newagents for securing, washing, detergent and like purposes.

Broadly, the invention relates to the use of sulphonated alkylatedaromatic compounds and their metallic salts, preferably the inorganicwater-soluble salts, wherein said aliphatic group is obtainable from ahalogenated gasoline or kerosene fraction and preferably a gasoline orkerosene fraction having a distilling range of substantially 180 C. to280 C. More particularly the present invention relates to detergents,scouring and washing agents and the like comprising sulphonatedalkylated aromatic compounds and preferably aromatic hydrocarbons, asfor example benzene, toluene, naphthalene, diphenyl, chlordiphenyl, monochlorbenzene and the like wherein said aliphatic group contains morethan ten and less than sixteen carbon atoms, and more particularlywherein said aliphatic group contains fourteen carbon atoms.

The compounds of the present invention may be used alone or incombination with other suitable detergents for cleansing and scouringVegetable and animal fibers, when removing fatty or oily materials. Theymay be used in the washing of fruits and vegetables for spray residueremoval.

As embodiments of the broader aspects of the invention kerosene wasdistilled and fractions collected having the distilling ranges of 140 C.to 162 0., 162 C. to 182 C., 182 C. to 204.5 C., 204.5 C. to 224.5 C.,224.5 C. to 244C 244 C. to 260 C. and 260 C. to 280 C., said fractionscorresponding to the boiling points of nonane,

decane, undecane, dodecane, tridecane, tetradecane and pentadecanerespectively. The distillates so obtained were halogenated by means of asuitable halogen, for example chlorine, the

halide so obtained condensed with an aromatic compound, for examplebenzene, toluene, naphthalene, diphenyl, chlordiphenyl, monochlorbenzene and the like and the product so obtained sulphonated bymeans of a suitable sulphonating agent, and the sulphonic acid isolatedpreferably as the alkali metal salt.

As illustrative of the above process three molecular proportions ofhydrocarbon distilling between substantially 244" C. and 260 C. aresubstantially one-third chlorinated on a molar basis.

The product so obtained is treated with substantially 6.4 molecularproportions of benzene in the presence of aluminum chloride and aFriedel- Crafts synthesis carried out, after which the unreacted benzeneand unchlorinated hydrocarbon are removed preferably by fractionationfrom the alkyl benzene. Substantially 50 parts by weight of the alkylbenzene so obtained and substantially 10 parts by weight of 95%sulphuric acid are placed in a suitable reactor and substantially partsby weight of 25% oleum added slowly thereto, preferably with cooling.After the reaction is completed, water is added to effect separation ofthe major portion of the spent acid, which is drawn off, and the upper10 layer comprising the alkyl benzene sulphonic acid is preferablyconverted to the desired metal salt.

Other methods of preparing the preferred class of compounds may, ofcourse, be employed as is obvious to those skilled in the art. Thus, itis 15 obvious that other sulphonating agents, as for examplechlor-sulphonic acid may be employed.

The metallic salts of the alkylated and sulphonated benzenes employingthe kerosene fractions given above have all been prepared in a 20 manneranalogous to that hereinbefore described and tested for detergent andwashing properties employing the following procedure.

Portions of woolen cloth weighing 5 grams and measuring 7 x 7 andcontaining not in 25 excess of 0.2% of ether extractable material areimpregnated with 5.0% by weight of paraffin oil by means of an ethersolution thereof. After removal of the ethereal solvent byvolatilization, the test strips are placed in glass jars of 500 c. c. 30capacity containing 200 c. c. of an aqueous solution of 1 gram ofdetergent and a sufiicient number of Monel metal balls added to effectagitation of the liquid within the jars. The jars are immersed in watermaintained at 50 C. and agi- 35 tated by a suitable shaking machine.After scouring for one hour, the test strips are removed from the jarsand thoroughly washed with water, dried and extracted with ether in aSoxhlet extractor. On evaporating the ether 40 from the etherealextract, the percentage of residual oil is a measure of the efficiencyof the detergent action on the cloth.

The sodium salts of the alkylated and sulphonated benzenes abovedescribed were found to 45 be efficient cleansing agents.

As further specific embodiments of the present invention toluene,xylene, naphthalene, diphenyl, chlordiphenyl and mono chlor benzene havebeen reacted with the halogenated kerosene 5O distillates exemplifiedabove, for example the alkyl halide prepared from the kerosenedistillate having a distilling range of 162 to 182 C., and the alkylatedhydrocarbon after sulphonating, found, on testing,.to function asdesirable and 55 valuable washing, cleansing and emulsifying agents.Further, diphenyl and chlordiphenyl have been reacted with the alkylhalide prepared from a kerosene distillate having a distilling range of182 to 204.5 C. and the alkylated compound, after sulphonating, found topossess desirable detergent action.

As a preferred embodiment of the present invention aliphatichydrocarbons have been prepared by careful refractionation of cutsobtained from commercial kerosene. The octane, nonane, decane, undecane,dodecane, tridecane, tetradecane, pentadecane and hexadecane fractionsso prepared were halogenated by means of chlorine, and the halide soformed condensed with an aromatic hydrocarbon for example benzene in thepresence of aluminum chloride as a catalyst and the alkyl benzenesulphonated in a manner analogous to that employed above in thepreparation of an alkylated'sulphonated aromatic compound employinghalogenated kerosene cuts as the alkylating agent.

Heretofore, certain sulphonated alkylated aromatic hydrocarbons havebeen employed as detergents, cleansing and emulsifying agents. Accordingto the present invention it has been discovered, however, that the mostefiicient detergent, cleansing and like action are present in thosesulphonated alkylated aromatic compounds which contain more than ten andless than sixteen carbon atoms in the side chain. This is demonstratedand will be evident from the following data wherein the cleansing actionof the sodium salts of the sulphonated alkylated benzenes containingeight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteenand twenty-three carbon atoms in the side chain are compared by testingaccording to the method of detergency hereinbefore defined.

Table I Percent Dete residual oil It is thus clearly shown that the useof salts of sulphonated alkylated aromatic compounds containing morethan ten and less than sixteen carbon atoms in the side chain aswashing, detergent and emulsifying agents comprises an important advancein the art.

What is claimed is:

1. A detergent comprising essentially a mixture of mono-sulphonatedalkylated benzene hydrocarbons obtained by substantially one-thirdchlorinating on a molar basis a kerosene fraction selected from akerosene having a distilling range of substantially 182 C. to 280 C. andconsisting substantially of paraffinic hydrocarbons, the majorproportion of which is selected from the group consisting of undecane,dodecane, tridecane, tetradecane and pentadecane, employing saidchlorinated hydrocarbons as an alkylation medium by condensing anaromatic hydrocarbon of the benzene series therewith by a Friedel-Crafts synthesis in the presence of aluminum chloride, separating thealkylated benzene hydrocarbons therefrom, and sulphonating the alkylatedbenzene hydrocarbons so obtained.

2. A method of preparing a detergent which comprises chlorinating akerosene fraction consisting substantially of paraiiinic hydrocarbonshaving more than ten and less than sixteen carbon atoms and having adistilling range of substantially 182 to 280 C. by the introduction ofchlorine into an excess of said kerosene so as to produce a preponderantquantity of alkyl monochlorides, employing said alkyl monochlorides asan alkylation medium by condensing an aromatic hydrocarbon of thebenzene series therewith by means of a Friedel-Craft synthesis andsulphonating the condensation product to form the monosulphonic acidsthereof.

3. A detergent comprising essentially a mixture of water-soluble saltsof mono-sulphonated alkylated benzene compounds obtained by introducingchlorine into an excess of a paraffin base kerog ene fraction consistingsubstantially of paraffinic hydrocarbons, the major proportion of whichis selected from the group consisting of undecane, dodecane, tridecane,tetradecane and pentadecane and having a distilling range ofsubstantially 182 C. to 289 C. so as to produce a preponderantproportion of alkyl monochlorides, employing said alkyl monochlorides asan alkylation medium by condensing an aromatic hydrocarbon of thebenzene series therewith, sulphonating the alkylated benzene compoundsand. converting the sulphonic acids to the alkali metal salts.

4. A detergent comprising essentially a mixture of water soluble saltsof mono-sulphonated,

mono-alkylated benzene compounds obtained by introducing chlorine intoan excess of a kerosene fraction consisting substantially of paraflinichydrocarbons, the major proportion of which is selected from the groupconsisting of undecane, dodecane, tridecane, tetradecane and pentadecaneand having a distilling range of substantially 182 C. to 280 C'., so asto produce a preponderant proportion of alkyl monochlorides, employingsaid alkyl monochlorides as an alkylation medium by condensing asubstantial molecular excess, based on the alkyl monochlorides present,of an aromatic hydrocarbon of the benzene series therewith to obtainsubstantially monoalkylated benzene compounds, sulphonating saidmonoalkylated benzene compounds and converting the sulphonic acids tothe alkali metal salts.

5. A detergent comprising essentially a mixture of mono-sulphonatedalkylated benzene compounds obtained by introducing chlorine into anexcess of a kerosene fraction consisting substantially of parafiinichydrocarbons and having a distilling range of substantially 224.5 C. to244 C. so as to produce a preponderant proportion of alkylmonochlorides, employing said alkyl chlorides as an alkylation medium bycondensing therewith an aromatic hydrocarbon of the benzene series andsulphonating the alkylated benzene compounds.

6. A detergent comprising essentially a mixture of mono-sulphonatedalkylated benzene com pounds obtained by introducing chloride into anexcess of a kerosene fraction consisting substan tially of paraffinichydrocarbons and having a distilling range of substantially 244 C. to260 C. so as to produce a preponderant proportion of alkylmonochlorides, employing said alkyl monochlorides as an alkylationmedium by condensing an aromatic hydrocarbon of the benzene seriestherewith and sulphonating the alkylated ben- Zene compounds.

7. A detergent comprising essentially a mixture of mono-sulphonatedalkylated benzene compounds obtained by introducing chlorine into anexcess of a kerosene fraction consisting substantially of paraffinichydrocarbons and having a distilling range of substantially 260 C. to280 C. so as to produce a 'preponderant proportion of alkylmonochlorides, employing said alkyl monochlorides as an alkylationmedium by condensing an aromatic hydrocarbon of the benzene seriestherewith and sulphonating the alkylated benzene compounds.

8. A detergent comprising essentially a mixture of water soluble saltsof mono-sulphonated alkylated benzene compounds obtained by introducingchlorine into an excess of a kerosene fraction consisting substantiallyof paraffinic hydrocarbons and having a distilling range ofsubstantially 224.5 C. to 244 C. so as to produce a preponderantproportion of alkyl monochilorides, employing said alkyl monochloridesas an alkylation medium by condensing therewith an arcmatic hydrocarbonof the benzene series, sulphonating the alkylated benzene hydrocarbonsand converting the sulphonic acids to the alkali metal salts.

9. A detergent comprising essentially a mixture of Water soluble saltsof mono-sulphonated alkylated benzene compounds obtained by introducingchlorine into an excess of a paraffin base kerosene fraction consistingsubstantially of paraifinic hydrocarbons and having a distilling rangeof substantially 244 C. to 260 C. so as to produce a preponderantproportion of alkyl monochlorides, employing said alkyl monochlorides asan alkylation medium by condensing therewith an aromatic hydrocarbon ofthe benzene series, sulphonating the alkylated benzene hydrocarbons andconverting the sulphonic acids to the alkali metal salts.

10. A detergent comprising essentially a mixture of water soluble saltsof mono-sulphonated alkylated benzene compounds obtained by introducingchlorine into an excess of a paraffin base kerosene fraction consistingsubstantially of parafiinic hydrocarbons and having a distilling rangeof substantially 260 C. to 280 C. so as to produce a preponderantproportion of alkyl monochlorides, employing said alkyl monochlorides asan alkylation medium by condensing an aromatic hydrocarbon of thebenzene series therewith, sulphonating the alkylated benzenehydrocarbons and converting the sulphonic acids to the akali metalsalts.

11. A detergent comprising essentially a mixture of alkali metal saltsof mono-sulphonated alkylated benzene hydrocarbons obtained byintroducing chlorine into an excess of a kerosene fraction consistingsubstantially of paraffinic hydrocarbons, the major proportion of whichis selected from the group consisting of undecane, dodecane, trideoane,tetradecane and pentadecane, and having a distilling range ofsubstantially 182 C. to 280 C. so as to produce a preponderantproportion of alkyl monochlorides, employing said alkyl monochlorides asan alkylation medium by condensing an aromatic hydrocarbon of thebenzene series therewith, separating the alkylated benzene hydrocarbonsthere from, sulphonating the alkylated benzene hydrocarbons, addingwater to the sulphonatcd reaction products to form an upper layer of thealkylated benzene sulphonic acids and a lower aqueous layer containingthe major portion of the spent sulphonating agent, withdrawing the lowerlayer and neutralizing the upper layer of reaction products to form thealkali metal salts.

12. A detergent comprising essentially a mixture of water-soluble saltsof benzene mono-sulphonic acids having a nuclear hydrogen substituted byan alkyl radical obtained by introducing chlorine into an excess of aparaffinic base kerosene fraction consisting substantially of parafiiniehydrocarbons, the major proportion of which is a tridecane, and having adistilling range of substantially 224.5 C. to 244 C., so as to produce apreponderant proportion of alkyl monochlorides,

employing said alkyl monochlorides as an alkylation medium by condensingbenzene therewith, sulphonating the alkylated benzenes and convertingthe sulphonic acids to the alkali metal salts.

13. A detergent comprising essentially a mixture of water-soluble saltsof benzene monosulphonic acids having a nuclear hydrogen substituted byan alkyl radical obtained by introducing chlorine into an excess of aparafiin base kerosene fraction consisting substantially of paraffinichydrocarbons, the major proportion of which is a tetradecane, and havinga distilling range of substantially 244 C. to 260 C. so as to produce apreponderant proportion of alkyl monochlorides, employing said alkylmonochlorides as an alkylation medium by condensing benzene therewith,sulphonating the alkylated benzenes and converting the sulphonio acidsto the alkali metal salts.

14. A detergent comprising essentially a mixture of water-soluble saltsof benzene mono-sulphonic acids having a nuclear hydrogen substituted byan alkyl radical obtained by introducing chlorine into an excess of aparaffin base kerosene fraction consisting substantially of parafiinichydrocarbons, the major proportion of which is a pentadecane, and havinga distilling range of substantially 260 C. to 280 C. so as to produce apreponderant proportion of alkyl monochlorides, employing said alkylmonochlorides as an alkylation medium by condensing benzene therewith,sulphonating the alkylated benzenes and converting the sulphonic acidsto the alkali metal salts.

LUCAS P. KYRIDES.

